Polycyclic dyes

ABSTRACT

A polycyclic dye of the Formula (1): ##STR1## wherein: Ring A is unsubstituted or is substituted by from 1 to 3 groups; 
     R 1  is cycloalkyl; 
     m is 0, 1, 2 or 3; 
     n is 0 or 1; 
     p is 0, 1, 2 or 3; and 
     Ring B is unsubstituted apart from the --O(CH 2 ) m  (CO 2 ) n  (CH 2 ) p  --R 1  or is substituted by from 1 to 4 further groups. 
     The dyes are useful for the coloration of textile materials particularly synthetic textiles such as polyester.

This specification describes an invention which relates to polycyclic dyes.

According to the present invention there is provided a polycyclic dye of the Formula (1): ##STR2## wherein: Ring A is unsubstituted or is substituted by from 1 to 3 groups;

R¹ is cycloalkyl;

m is 0, 1, 2 or 3;

n is 0 or 1;

p is 0, 1, 2 or 3; and

Ring B is unsubstituted apart from the --O(CH₂)_(m) (CO₂)_(n) (CH₂)_(p) --R¹ or is substituted by from 1 to 4 further groups.

Suitable further substituents for Ring B are preferably selected from --OH, halogen, nitro, alkyl, alkoxy, alkenyl, aryl, alkoxyalkyl, alkoxyalkoxy, alkoxycarbonylalkoxy, alkoxyalkoxycarbonylalkoxy, alkylcarbonyloxyalkoxy, aryloxy, alkylcarbonyl, alkylsulphonyl, CN-alkoxy, HO-alkoxy, HO₂ C-alkoxy, alkylthio, arylthio and --NR² R³ in which R² and R³ are each independently --H, alkyl or alkenyl.

Suitable substituents for Ring A are those listed for Ring B above and --O(CH₂)_(m) (CO₂)_(n) (CH₂)_(p) --R¹ in which m, n, p and R¹ are as hereinbefore defined.

In the substituents for Ring A and Ring B it is preferred that the alkyl or alkoxy parts of the substituents are C₁₋₄ -alkyl or C₁₋₄ -alkoxy respectively, the alkenyl is C₃₋₄ -alkenyl, the aryl is phenyl or naphthyl, and the halogen is --F, --Cl or --Br. Preferred substituents for Ring A are C₁₋₄ -alkyl, C₁₋₄ -alkoxy, --NH₂ or --NHC₁₋₄ -alkyl. Especially preferred substituents for Ring A are C₁₋₄ -alkyl, C₁₋₄ -alkoxy, --NH₂ and --NHC₁₋₄ -alkyl in the 4-position and --H or C₁₋₄ -alkyl in the 3-position. Where Ring A is substituted by one further substituent it is preferred that this is in the 3-, 4- or 5-position, more preferably in the 4-position. Where Ring A is substituted by two further substituents it is preferred that these are in the 3- and 4-positions, and where there are three further substituents it is preferred that these are in the 3-, 4- and 5-positions. Ring B is preferably unsubstituted, apart from the --O(CH₂)_(m) (CO₂)_(n) (CH₂)_(p) --R¹ group, or is substituted by one or two further substituents and these substituents are preferably in the 3- or in the 3- and 5-positions.

The alkyl or alkoxy substituents suitable for Ring A and Ring B may be straight or branched chain.

The cycloalkyl group represented by R¹ is preferably a C₃₋₈ -cycloalkyl group, more preferably C₅₋₇ -cycloalkyl and especially cyclohexyl. The cycloalkyl group represented by R¹ may be substituted by at least one group selected from C₁₋₆ -alkyl, C₁₋₆ -alkoxy, hydroxy, cyano, halogen, such as --Cl and --F, nitro, C₁₋₄ -alkoxy-C₁₋₄ -alkoxy, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkoxycarbonyl, C₁₋₄ -alkoxy-C₁₋₄ -alkoxycarbonyl, C₁₋₄ -alkylcarbonyloxy, C₁₋₄ -alkoxycarbonyloxy, C₁₋₄ -alkoxy-C₁₋₄ -alkoxycarbonyloxy, phenyl, amino, C₁₋₄ -alkylamino and di(C₁₋₄ -alkyl)amino.

A preferred sub-group of compounds of Formula (1) are those in which m is from 1 to 3, n is 1, p is from 1 to 3, and R¹, Ring A and Ring B are as hereinbefore defined. A further preferred sub-group of compounds of Formula (1) are those in which m is from 1 to 3, n is 0, p is from 1 to 3, and R¹, Ring A and Ring B are as hereinbefore defined.

Especially preferred compounds of Formula (1) are those in which R¹ is cyclohexyl, Ring A is unsubstituted or is substituted by C₁₋₄ -alkoxy, m is 1 or 2, n is 1 and p is from 1 to 3 and those in which R¹ is cyclohexyl, Ring A is unsubstituted or is substituted by C₁₋₄ -alkoxy, m is from 1 to 3, n is 0 and p is 0.

The compounds of Formula (1) in which n is 1 may be prepared by esterification of the corresponding carboxylic acid to that of Formula I in which --(CH₂)_(p) --R¹ is replaced by H with for example an alcohol of formula HO(CH₂)_(p) --R¹ in which p and R¹ are as hereinbefore defined. The compounds of Formula (1) in which n is 0 may be prepared by alkylation of the corresponding hydroxy compound to that of Formula I in which --(CH₂)_(m) (CO₂)_(n) (CH₂)_(p) --R¹ is replaced by H in an aprotic solvent such as dimethylformamide or sulpholane with an alkylating agent such as a mesylate of formula MeSO₂ O(CH₂)_(m) (CH₂)_(p) --R¹, in which Me is methyl and m, p and R¹ are as hereinbefore defined.

The carboxylic acid and hydroxy compounds referred to above may be prepared by methods described in EP 0033583B and 0146269B and in EP 0363034A.

Compounds of Formula (1) give yellowish-red to bluish-red shades when applied to synthetic fibers or mixtures thereof, especially polyesters by disperse dyeing processes. The compounds of Formula (1) exhibit excellent fastness properties.

The invention is further illustrated by the following examples:

EXAMPLE 1

(i) A mixture of hydroquinone (15 g), mandelic acid (15 g), acetic acid (95 cm³) and sulphuric acid (5 cm³) was stirred at ambient temperature before filtering off solid material. The solid was washed with water and dried to give 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran (14 g, 65%).

(ii) A mixture of 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran (14 g), 4-carboxymethoxymandelic acid (18 g), acetic acid (100 cm³) and sulphuric acid (100 cm³) was heated at 110° C. for 18 hours before cooling. Ammonium persulphate (13.5 g) was added and the mixture heated at 110° C. for 1 hour. The reaction mixture was cooled and poured into a mixture of ice and water, the precipitated solid was filtered off, washed with water and methanol and dried to give 3-phenyl-7-(4-(carboxymethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (10.5 g, 45%).

(iii) A mixture of 3-phenyl-7-(4-(carboxymethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (2 g), cyclohexylmethanol (20 cm³) and sulphuric acid (98%, 0.25 cm³) was heated at 180° C. for 11/2 hours. The reaction mixture was cooled, the precipitated solid was filtered off, washed with methanol and dried. The dried solid was recrystallised from toluene to give 3-phenyl-7-(4-(cyclohexylmethoxycarbonylmethoxy) phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (1.6 g, 65%). λ_(max) in dichloromethane=488 nm.

EXAMPLE 2

The procedure of Example 1(iii) was followed except that 2-(cyclohexyl)ethanol was used in place of the cyclohexylmethanol. 3-Phenyl-7-(4-(2-cyclohexylethoxycarbonylmethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (2 g, 79%) was obtained. λ_(max) in dichloromethane=484 nm.

EXAMPLE 3

The procedure of Example 1(iii) was followed except that 3-(cyclohexyl)propanol was used in place of the cyclohexylmethanol. 3-Phenyl-7-(4-(3-cyclohexylpropoxycarbonylmethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (1.8 g, 69%) was obtained. A λ_(max) in dichloromethane=484 nm.

EXAMPLE 4

(i) The procedure of Example 1(i) was followed except that 4-(n-propoxy)mandelic acid was used in place of mandelic acid. 5-Hydroxy-2-oxo-3-(4-n-propoxyphenyl)-2,3-dihydrobenzofuran was obtained.

(ii) The procedure of Example 1(ii) was followed except that 4-(n-propoxy)mandelic acid was used in place of mandelic acid. 5-hydroxy-2-oxo-3-(4-(n-propoxy)phenyl)-2,4-dihydrobenzofuran was used obtained.

(ii) The procedure of Example 1(ii) was followed except that 5-hydroxy-2-oxo-3-(4-(n-propoxy)phenyl)-2,4-dihydrobenzofuran was used in place of 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran. 3-(4-(n-Propoxy)phenyl)-7-(4-(carboxymethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran was obtained.

(iii) The procedure of Example 1(iii) was followed except that 3-(4-(n-propoxy)phenyl)-7-(4-(carboxymethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (3 g) was used in place of the 3-phenyl-7-(4-(carboxymethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran. 3-(4-(n-Propoxy)phenyl)-7-(4-(cyclohexylmethoxycarbonylmethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (2 g, 56%) was obtained λ_(max) in dichloromethane=518 nm.

EXAMPLE 5

The procedure of Example 4 was followed except that 2-(cyclohexyl)ethanol was used in place of the cyclohexylmethanol. 3-(4-(n-Propoxy)phenyl)-7-(4-(2-cyclohexylethoxycarbonylmethoxy)phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (2.1 g, 57%) was obtained. λ_(max) in dichloromethane=519 nm.

EXAMPLE 6

The procedure of Example 4 was followed except that 3-(cyclohexyl)propanol was used in place of the cyclohexylmethanol. 3-(4-(n-Propoxy)phenyl)-7-(4-(3-cyclohexylpropoxycarbonylmethoxy) phenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (2.2 g, 58%) was obtained. λ_(max) in dichloromethane=518 nm .

EXAMPLE 7

A mixture of 3-phenyl-7-(4-hydroxyphenyl)-2,6-dioxo-2,6-dihydrobenzo-[1:2-b, 4:5-b']difuran (5 g), potassium carbonate (1.9 g), cyclohexylpropylmesylate (3 g) and sulpholane (100 cm³) were stirred at ambient temperature before heating at 160° C. for 1/2 hour. The reaction mixture was cooled, water was added and the precipitated solid filtered off, washed with water and dried. The dry solid was dissolved in dichloromethane and the resultant solution was filtered to remove insoluble matter before purification by elution from silica and recrystallising from toluene. 3-Phenyl-7-(4-(3-cyclohexylpropoxy) phenyl)-2,6-dioxo-2,6-dihydrobenzo[1:2-b, 4:5-b']difuran (1.5 g, 22%) was obtained. A λ_(max) in dichloromethane=500 nm.

EXAMPLES 8-25

The procedure of Example 1 was used to prepare the following dyes of Formula (2):

    ______________________________________                                          ##STR3##                 Formula (2)                                          EXAM-                                                                          PLE    R.sup.1       R.sup.5   R.sup.6                                                                              λ max nm                           ______________________________________                                          8                                                                                     ##STR4##     OC.sub.2 H.sub.5                                                                         H     516                                        9                                                                                     ##STR5##     CH.sub.3  H     500                                       10                                                                                     ##STR6##     NH.sub.2  H     572                                       11                                                                                     ##STR7##     NH.sub.2  CH.sub.3                                                                             570                                       12                                                                                     ##STR8##     NHC.sub.2 H.sub.5                                                                        CH.sub.3                                                                             621                                       13                                                                                     ##STR9##     OC.sub.2 H.sub.5                                                                         CH.sub.3                                                                             520                                       14                                                                                     ##STR10##    OC.sub.2 H.sub.5                                                                         H     513                                       15                                                                                     ##STR11##    CH.sub.3  H     498                                       16                                                                                     ##STR12##    NH.sub.2  H     571                                       17                                                                                     ##STR13##    NHC.sub.2 H.sub.5                                                                        CH.sub.3                                                                             618                                       18                                                                                     ##STR14##    OC.sub.2 H.sub.5                                                                         CH.sub.3                                                                             519                                       19                                                                                     ##STR15##    NH.sub.2  CH.sub.3                                                                             567                                       20                                                                                     ##STR16##    OC.sub.2 H.sub.5                                                                         H     517                                       21                                                                                     ##STR17##    CH.sub.3  H     501                                       22                                                                                     ##STR18##    NH.sub.2  H     569                                       23                                                                                     ##STR19##    NH.sub.2  CH.sub.3                                                                             570                                       24                                                                                     ##STR20##    NHC.sub.2 H.sub.5                                                                        CH.sub.3                                                                             619                                       25                                                                                     ##STR21##    OC.sub.2 H.sub.5                                                                         CH.sub.3                                                                             518                                       ______________________________________                                          ##STR22##                                                                

EXAMPLES 26-40

The procedure of Example 7 was used to prepare the following dyes of Formula (3):

    ______________________________________                                          ##STR23##                Formula (3)                                          EXAM-                                                                          PLE    R.sup.1       R.sup.8   R.sup.9                                                                              λ max nm                           ______________________________________                                         26                                                                                     ##STR24##    OC.sub.3 H.sub.7                                                                         H     533                                       27                                                                                     ##STR25##    H         H     499                                       28                                                                                     ##STR26##    CH.sub.3  H     510                                       29                                                                                     ##STR27##    NH.sub.2  H     578                                       30                                                                                     ##STR28##    NH.sub.2  CH.sub.3                                                                             580                                       31                                                                                     ##STR29##    H         H     499                                       32                                                                                     ##STR30##    OC.sub.3 H.sub.7                                                                         H     537                                       33                                                                                     ##STR31##    CH.sub.3  H     512                                       34                                                                                     ##STR32##    NH.sub.2  H     579                                       35                                                                                     ##STR33##    NH.sub.2  CH.sub.3                                                                             582                                       36                                                                                     ##STR34##    OC.sub.3 H.sub.7                                                                         H     539                                       37                                                                                     ##STR35##    CH.sub.3  H     512                                       38                                                                                     ##STR36##    NH.sub.2  H     580                                       39                                                                                     ##STR37##    NH.sub.2  CH.sub.3                                                                             581                                       40                                                                                     ##STR38##    NHC.sub.2 H.sub.5                                                                        CH.sub.3                                                                             616                                       ______________________________________                                          ##STR39##                                                                 

I claim:
 1. A polycyclic dye of the Formula (1): ##STR40## wherein: Ring B is unsubstituted apart from the --O(CH₂)_(m) (CO₂)_(n) (CH₂)_(p) --R¹ or is substituted by from 1 to 4 further groups selected from the group consisting of --OH, --F, --Cl, --Br, nitro, C₁₋₄ -aklyl, C₁₋₄ -alkoxy, C₃₋₄ -alkenyl, phenyl, naphthyl, C₁₋₄ -alkoxyC₁₋₄ alkyl, C₁₋₄ -alkoxyC₁₋₄ -alkoxy, C₁₋₄ -alkoxycarbonylC₁₋₄ -alkoxy, C₁₋₄ -alkoxyC₁₋₄ -alkoxy carbonylC₁₋₄ -alkoxy, C₁₋₄ -alkylcarbonyloxyC₁₋₄ -alkoxy, phenoxy, naphthoxy, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkylsulphonyl, CN--C₁₋₄ -alkoxy, HO--C₁₋₄ -alkoxy, HO₂ C--C₁₋₄ -alkoxy, C₁₋₄ -alkylthio, phenylthio, naphthylthio and --NR² R³ in which R² and R³ are each independently --H, C₁₋₄ -alkyl or C₃₋₄ alkenyl,R¹ is C₃₋₈ -cycloakyl; m is from 1 to 3; n is 1; p is from 1 to 3; and Ring A is unsubstituted or is substituted by from 1 to 3 groups selected from any of the substituents defined for Ring B above and the group --O(CH₂)_(m) '(CO₂)_(n) '(CH₂)_(p) '--R¹ in which m' is 0, 1, 2 or 3, n' is 0 or 1, p' is 0, 1, 2 or
 3. 2. A polycyclic dye of the Formula (1): ##STR41## wherein: Ring B is unsubstituted apart from the --O(CH₂)_(m) (CO₂)_(n) (CH₂)_(p) --R¹ or is substituted by from 1 to 4 further groups selected from the group consisting of --OH, --F, --Cl, --Br, nitro, C₁₋₄ -aklyl, C₁₋₄ -alkoxy, C₃₋₄ -alkenyl, phenyl, naphthyl, C₁₋₄ -alkoxyC₁₋₄ -alkyl, C₁₋₄ -alkoxyaC₁₋₄ -alkoxy, C₁₋₄ -alkoxycarbonylC₁₋₄ -alkoxy, C₁₋₄ -alkoxyC₁₋₄ -alkoxy carbonylC₁₋₄ -alkoxy, C₁₋₄ -alkylcarbonyloxyC₁₋₄ -alkoxy, phenoxy, naphthoxy, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkylsulphonyl, CN--C₁₋₄ -alkoxy, HO--C₁₋₄ -alkoxy, HO₂ C--C₁₋₄ -alkoxy, C₁₋₄ -alkylthio, phenylthio, naphthylthio and --NR² R³ in which R² and R³ are each independently --H, C₁₋₄ -alkyl or C₃₋₄ alkenyl,R¹ is C₃₋₈ -cycloakyl; m is from 1 to 3; n is 0; p is from 1 to 3; and Ring A is unsubstituted or is substituted by from 1 to 3 groups selected from any of the substituents defined for Ring B above and the group --O(CH₂)_(m) '(CO₂)_(n) '(CH₂)_(p) '--R¹ in which m' is 0, 1, 2 or 3, n' is 0 or 1, p' is 0, 1, 2 or
 3. 3. A polycyclic dye according to claim 1 wherein R¹ is cyclohexyl, Ring A is unsubstituted or is substituted by C₁₋₄ -alkoxy, m is 1 or 2, n is 1 and p is from 1 to
 3. 4. A polycyclic dye of the Formula (1): ##STR42## wherein Ring B is unsubstituted apart from the --O(CH₂)_(m) (CO₂)_(n))(CH₂)_(p) --R¹ or is substituted by from 1 to 4 further groups selected from the group consisting of --OH, --F, --Cl, --Br, nitro, C₁₋₄ -aklyl, C₁₋₄ -alkoxy, C₃₋₄ -alkenyl, phenyl, naphthyl, C₁₋₄ -alkoxyC₁₋₄ -alkyl, C₁₋₄ -alkoxyaC₁₋₄ -alkoxy, C₁₋₄ -alkoxycarbonylC₁₋₄ -alkoxy, C₁₋₄ -alkoxy carbonylC₁₋₄ -alkoxy, C₁₋₄ -alkylcarbonyloxyC₁₋₄ -alkoxy, phenoxy, napthoxy, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkylsulphonyl, CN--C₁₋₄ -alkoxy, HO--C₁₋₄ -alkoxy, HO₂ C--C₁₋₄ -alkoxy, C₁₋₄ -alkylthio, phenylthio, naphthylthio and --NR² R³ in which R² and R³ are each independently --H, C₁₋₄ -alkyl or C₃₋₄ -alkenyl,R¹ is cyclohexyl; m is from 1 to 3; n is 0; p is 0; and Ring A is unsubstituted or is substituted by C₁₋₄ -alkoxy.
 5. A polycyclic dye according to claims 1 to 2 wherein R¹ is cycloalkyl substituted by at least one group selected from C₁₋₆ -alkyl, C₁₋₆ -alkoxy, hydroxy, cyano, --Cl, --F, nitro, C₁₋₄ -alkoxy-C₁₋₄ -alkoxy, C₁₋₄ -alkylcarbonyl, C₁₋₄ -alkoxycarbonyl, C₁₋₄ -alkoxy-C₁₋₄ -alkoxycarbonyl, C₁₋₄ -alkylcarbonyloxy, C₁₋₄ -alkoxycarbonyloxy, C₁₋₄ -alkoxy-C₁₋₄ -alkoxycarbonyloxy, phenyl, amino, C₁₋₄ -alkylamino and di(C₁₋₄ -alkyl)amino. 